arXiv subjects

Rohan Maniar

Publications and source records attributed to Rohan Maniar.

5 recordsLinked to original sources

arXiv2025

Effect of the Gradient of the Spin-Polarization in Density Functional Approximations

The construction of non-empirical density functional approximations is typically guided by the satisfaction of exact constraints. An important constraint is the recovery of the gradient expansion for slowly varying electron densities. In prior constructions of semilocal density functional approximations, the $\nabla \zeta$-dependent terms in the gradient expansion of the correlation have been dropped, where $\zeta$ is the relative spin polarization. We propose a scheme by which such terms can be reintroduced into already constructed functionals without significantly affecting other constraints and norms. We implement this scheme on the Strongly Constrained and Appropriately Normed (SCAN) functional to construct a $\nabla \zeta$-corrected version of SCAN. The resulting functional is shown to provide improvements in transition-metal atoms and molecules without significantly affecting SCAN's accurate description of $sp$-systems. For the binding energy curve of the chromium dimer Cr$_2$, the SCAN underbinding is fully corected at large bond lengths and reduced at short bond lengths.

physics.chem-ph↗

arXiv2025

Electron Localization in Non-Compact Covalent Bonds Captured by the r2SCAN+V Approach

In density functional theory, the SCAN (Strongly Constrained and Appropriately Normed) and r2SCAN functionals significantly improve over generalized gradient approximation functionals such as PBE (Perdew-Burke-Ernzerhof) in predicting electronic, magnetic, and structural properties across various materials, including transition-metal compounds. However, there remain puzzling cases where SCAN and r2SCAN underperform, such as in calculating the band structure of graphene, the magnetic moment of Fe, the potential energy curve of the Cr2 molecule, and the bond length of VO2. This research identifies a common characteristic among these challenging materials: non-compact covalent bonding through s-s, p-p, or d-d electron hybridization. While SCAN and r2SCAN excel at capturing electron localization at local atomic sites, they struggle to accurately describe electron localization in non-compact covalent bonds, resulting in a biased improvement. To address this issue, we propose the r2SCAN+V approach as a practical modification that improves accuracy across all the tested materials. The parameter V is 4 eV for metallic Fe, but substantially lower for the other cases. Our findings provide valuable insights for the future development of advanced functionals.

cond-mat.mtrl-sci↗

arXiv2025

{\Delta}SCF Excitation Energies Up a Ladder of Ground-State Density Functionals

Density functional theory (DFT) is a widespread and effective tool in electronic structure calculations for ground-state electron systems. Its success has prompted exploration into the use of DFT for non-collective excited states. The delta self-consistent field ($\Delta$SCF) method allows for the extension of DFT to excited-state energies by restricting the Kohn-Sham orbital occupations, producing an excited-state electron density, and then computing its energy. In this paper, we examine the performance of the LSDA, PBE generalized-gradient approximation (GGA), and SCAN/r2SCAN meta-GGA for the excitation energies of several important systems. We consider the energies of atoms with atomic number 1-18. For the hydrogen atom, where we use the exact electron density and have no multiplet splitting, we find significant improvement up the ladder from LSDA to PBE to SCAN. For the uniform gas, we find an effective mass different from the bare mass only with r2SCAN. We split the case of multi-electron atoms into non-aufbau excitations, where the highest-energy electron is excited to the lowest state in the next nl subshell (where accuracy is least limited by available basis sets), and spin-flip excitations, where the spin of an electorn is flipped, leading to a higher-energy state of the same nl configuration. We find reasonably accurate approximate excitation energies, except for the spin-flip cases where the auxiliary non-interacting wavefunction of a non-Hund's-rule spin state is not well-described by a single determinant.

physics.chem-ph↗

arXiv2024

Atomic Ionization: sd energy imbalance and Perdew-Zunger self-interaction correction energy penalty in 3d atoms

To accurately describe the energetics of transition metal systems, density functional approximations (DFAs) must provide a balanced description of s- and d- electrons. One measure of this is the sd transfer error, which has previously been defined as $E(\mathrm{3d}^{n-1}\mathrm{4s}^{1}) - E(\mathrm{3d}^{n-2}\mathrm{4s}^{2})$. Theoretical concerns have been raised about this definition due to its evaluation of excited-state energies using ground-state DFAs. A more serious concern appears to be strong correlation in the ${4s}^2$ configuration. Here we define a ground-state measure of the sd energy imbalance, based on the errors of s- and d-electron second ionization energies of the 3d atoms, that effectively circumvents the aforementioned problems. We find an improved performance as we move from LSDA to PBE to r$^2$SCAN for first-row transition metal atoms. However, we find large (~ 2 eV) ground-state sd energy imbalances when applying a Perdew-Zunger 1981 self-interaction correction. This is attributed to an "energy penalty" associated with the noded 3d orbitals. A local scaling of the self-interaction correction to LSDA results in a balance of s- and d-errors.

physics.chem-ph↗

arXiv2019

Random walk model for coordinate dependent diffusion in a force field

In this paper we develop a random walk model on lattice for coordinate dependent diffusion at constant temperature in contact with a heat bath. We employ here a coordinate dependent waiting time of the random walker to make the diffusivity coordinate dependent. The presence of a confining conservative force is modeled by appropriately breaking the isotropy of the jumps of the random walker to its nearest neighbors. We show that the equilibrium is characterized by the position distribution which is of modified Boltzmann form. We also show that, in such systems with coordinate dependent diffusivity, the modified Boltzmann distribution correctly captures the transition over a potential barrier as opposed to the Boltzmann distribution.

cond-mat.stat-mech↗